Multidimensional Attosecond Resonant X-Ray Spectroscopy of Molecules: Lessons from the Optical Regime

Mukamel, Shaul; Healion, Daniel; Zhang, Yu; Biggs, Jason D.

doi:10.1146/annurev-physchem-040412-110021

Cited by 187 publications

(169 citation statements)

References 153 publications

(149 reference statements)

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“…In the photon echo experiment, the pump pulse is split into two, pulses k 1 and k 2 , each of which interact with the system just once. Likewise the probe pulse is split into pulses k 3 and k 4 .…”

Section: Appendix A: Four-pulse Phase-matched K I and K Ii Signalsmentioning

confidence: 99%

Multidimensional x-ray spectroscopy of valence and core excitations in cysteine

Biggs

Zhang

Healion

et al. 2013

The Journal of Chemical Physics

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Several nonlinear spectroscopy experiments which employ broadband x-ray pulses to probe the coupling between localized core and delocalized valence excitation are simulated for the amino acid cysteine at the K-edges of oxygen and nitrogen and the K-and L-edges of sulfur. We focus on two-dimensional (2D) and 3D signals generated by two-and three-pulse stimulated x-ray Raman spectroscopy (SXRS) with frequency-dispersed probe. We show how the four-pulse x-ray signals k I = −k 1 + k 2 + k 3 and k II = k 1 − k 2 + k 3 can give new 3D insight into the SXRS signals. The coupling between valence-and core-excited states can be visualized in three-dimensional plots, revealing the origin of the polarizability that controls the simpler pump-probe SXRS signals.

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Section: Appendix A: Four-pulse Phase-matched K I and K Ii Signalsmentioning

confidence: 99%

Multidimensional x-ray spectroscopy of valence and core excitations in cysteine

Biggs

Zhang

Healion

et al. 2013

The Journal of Chemical Physics

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“…Optical Raman techniques have been applied to study electron transfer and nonadiabatic dynamics at conical intersections. Using recently developed FEL and HHG sources [17][18][19], Raman techniques can be further extended to the X-ray regime [20][21][22][23][24] whereby the system is initially prepared in the superposition of valence electronic states and an X-ray Raman probe then reveals information about electronic, rather than vibrational, coherence.…”

Section: Introductionmentioning

confidence: 99%

“…This paper presents several electronic Raman techniques performed with X-ray pulses that carry higher levels of information [21,27,28]. The same techniques apply to conventional vibrational Raman as well.…”

Section: Introductionmentioning

confidence: 99%

Detecting electronic coherence by multidimensional broadband stimulated x-ray Raman signals

2015

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Nonstationary molecular states which contain electronic coherences can be impulsively created and manipulated by using recently-developed ultrashort optical and X-ray pulses via photoexcitation, photoionization and Auger processes. We propose several stimulated-Raman detection schemes that can monitor the phase-sensitive electronic and nuclear dynamics. Three detection protocols of an X-ray broadband probe are compared -frequency dispersed transmission, integrated photon number change, and total pulse energy change. In addition each can be either linear or quadratic in the X-ray probe intensity. These various signals offer different gating windows into the molecular response which is described by correlation functions of electronic polarizabilities.Off-resonant and resonant signals are compared. * kdorfman@uci.edu 1 arXiv:1506.08226v1 [physics.chem-ph]

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“…Recent proposals for using nonlinear X-ray spectroscopy to study electronic dynamics in molecules involve the creation of coherent linear combinations of valence states using autoionizing, core excited states as intermediates [1][2][3]. This mechanism permits site specificity; the initial valence excitation is localized on the atomic center supporting the core excitation, and its subsequent evolution across the molecule may be probed by core transitions on other centers.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast population transfer to excited valence levels of a molecule driven by x-ray pulses

Haxton

McCurdy

2014

Phys. Rev. A

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First-principles quantum mechanical calculations of an intense-field ultrafast two-color core hole stimulated Raman process in nitric oxide are presented. They employ the Multiconfiguration TimeDependent Hartree-Fock (MCTDHF) method with all 15 electrons active. These calculations demonstrate a robust excitation localized on an atom through a core-electron stimulated Raman transition, the first step in proposed stimulated X-ray Raman spectroscopy experiments. A total population transfer of approximately 41% into valence excited states and 30% ionization is obtained via two concurrent 1.31fs pulses of maximum intensity 0.5 and 3 ×10 17 W cm −2 . It is found that both resonant and nonresonant (via the continuum) Raman transitions contribute. All aspects of these calculations except for AC stark shifts are converged with a modest basis of 11 orbitals, demonstrating the efficiency of MCTDHF for the treatment of nonperturbative electronic dynamics in molecules.

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Multidimensional Attosecond Resonant X-Ray Spectroscopy of Molecules: Lessons from the Optical Regime

Cited by 187 publications

References 153 publications

Multidimensional x-ray spectroscopy of valence and core excitations in cysteine

Multidimensional x-ray spectroscopy of valence and core excitations in cysteine

Detecting electronic coherence by multidimensional broadband stimulated x-ray Raman signals

Ultrafast population transfer to excited valence levels of a molecule driven by x-ray pulses

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